Laboratory Investigation of Diluted Bitumen Trapping and Dissolution in Gravel

The Canadian economy is largely dependent on the distribution of large volumes of oil to domestic and international markets by a long network of pipelines. Unfortunately, accidents occur, and oil can leak or spill from these pipelines before it reaches its destination. Of particular concern are the long-term consequences of oil spills in freshwater, which include sinking of oil in water and the contamination of sensitive areas, such as where fish (e.g., salmon) deposit their eggs in gravel-dominated river sediments. There is a knowledge gap regarding the fate and behaviour of oil in river sediment. To this end, this study aimed at finding the potential for diluted bitumen (dilbit) oil to become trapped in gravel and to transfer hydrocarbons into water by dissolution, which are harmful to aquatic life. Two sets of laboratory experiments were conducted to simulate conditions of an oil spill on an exposed bank or in shallow water. In the first set, by conducting capillary pressure-saturation (Pc-Sw) experiments it was found that dilbit can enter gravel pores without much resistance and approximately 14% of the pore volume can be occupied by discontinuous single or multipore blobs of dilbit following imbibition of water. Air-water Pc-Sw experiments done in laboratory 1-D columns required gravity correction and could be successfully scaled to predict dilbit-water Pc-Sw curves, except for the trapped amount of dilbit. Trapped dilbit constituents can be dissolved into the water flowing through gravel pores (hyporheic flow) at different velocities. In the second set, dissolution experiments suggested that for the duration of the test, hydrocarbons that cause acute toxicity dissolve rapidly, likely resulting in a decrease in their effective solubility. However, dilbit saturation changed only <2% within that time. Chronically toxic PAH compounds were also detected in the effluent water. The total concentration of all detected PAHs and alkylPAHs exceeded the threshold literature value to protect early-life stage fish. Observations of decreased concentrations with increased aqueous velocities as well as less than equilibrium concentrations indicated that the mass transfer was rate-limited. A correlation was developed for the mass transfer rate coefficient to understand the mass transfer behaviour beyond the conditions used in the experiments, which had a Reynolds number exponent similar to the studies of NAPL dissolution in groundwater.

Polystyrene and asphaltene micelles within blends with a bitumen of an SBS block copolymer and styrene and butadiene homopolymers

Using fluorescence microscopy, DSC and DMTA we have explored blends of a bitumen with a styrene-butadiene-styrene (SBS) block copolymer, and with blends of the bitumen with SBS and one or two homopolymers - a polystyrene and a poly(cis-butadiene). The SBS polymer was progressively replaced with quantities of the homopolymers both together in the proportions found in the block copolymer and then by each homopolymer separately. At low temperatures the blends are all softer than the bitumen itself, so the polymers plasticise the bitumen-rich phase, and above 50°C the blends' stiffness (E') falls below a plateau only when a critical proportion of the block copolymer has been replaced with the two homopolymers: this supports the idea of an extensive network created by the polystyrene-rich spherical microphases that is effective even when the polystyrene microphases have melted. In one polymer blend the stiffness rose as the temperature was raised above 100°C, suggesting the development of a mesophase based upon polybutadiene plus asphaltenes, in another E' was enhanced and E" remained constant as the temperature rose above 70°C, perhaps for a similar reason; in some loss process appeared and the stiffness fell as temperature rose; but in others a good part of the SBS was replaced by either polystyrene or polybutadiene without changing the appearance of a rubbery plateau, that is, without a diminution of the mechanical properties of the soft matter.

Elemental and isotope compositions of lipids, kerogens and asphaltenes from samples of DSDP Hole 41-368

The thermal effects of three (one major and two minor) Miocene diabase intrusions on Cretaceous black shales from DSDP site 41-368 have been analyzed. A concentration gradient was observed, especially for the hydrocarbons, decreasing towards the major intrusion and between the three sills. The thermally-altered samples in the proximity of and between the sills contained elemental sulfur and an excess of thermally-derived pristane over phytane. whereas, the unaltered sediments contained no elemental sulfur, and more phytane than pristane. A maximum yield of the extractable hydrocarbons was observed at a depth of 7 m below the major sill. Two classes of molecular markers were present in this bitumen suite. The first was sesqui-, di- and triterpenoids and steranes. which could be correlated with both terrigenous and autochthonous sources. They were geologically mature and showed no significant changes due to the thermal stress. The second class was found in the altered samples, which contained only polynuclear aromatic hydrocarbons with low alkyl substitution and sulfur and oxygen heterocyclic aromatic compounds. These compounds were derived from pyrolytic reactions during the thermal event. Kerogen was isolated from all of these samples, but only traces of humic substances were present. The H/C, N/C, d13C, d34S and dD all exhibit the expected effects of thermal stress. The kerogen becomes more aromatized and richer in 13C, 34S and D in the proximity of and between the sills. Maturation trends were also measured by the vitrinite reflectance and electron spin resonance, where the thermal stress could be correlated with an elevated country rock temperature and an increased degree of aromaticity. The effects of in situ thermal stress on the organic-rich shales resulted in the generation and expulsion of petroliferous material from the vicinity of the sills.

Bitumen and n-alkanes in organic matter from sedimentary rocks sampled in DSDP Holes 47-397A and 47-398

A study of samples from DSDP Leg 47 shows that transformation of organic matter in deep sea sediments is completly analogous to evolution of organic matter in sedimentary sequences on continents and depends on the same factors. Crucial among these factors are: genesis of organic matter, nature of its diagenetic changes, and current stage of catagenesis.

Thermal behaviour of bitumen modified by sulphur addition

The most frequent use of bitumen is as binder for pavement applications. The effect of sulphur addition on the properties of the bitumen has been extensively studied several decades ago. Recently, there is a renewed interest in researching the behaviour of sulphur-bitumen combination, because off 1.The future availability of bitumen may be limited and 2. The beneficial consumption of great amounts of sulphur compounds from petroleum refining is advisable. The addition of sulphur to bitumen provokes the beginning of chemical reactions depending on the sulphur content and heating temperature. At heating temperatures T< 140 ºC liquid sulphur reacts with naphthenic-aromatic fraction forming polysulphides. At temperatures above 150 ºC dehydrogenization reactions with emission of hydrogen sulfide take place and naphthenic-aromatic molecules are transformed into asphaltenes. Therefore, the addition of sulphur to bitumen provokes changes in the chemical structure of the bitumen. The objective of this work is to analyze, the thermal behaviour of sulphur-bitumen mixtures of different composition (0-35 %wt sulphur content) prepared at 130 and 140 ºC, by means of differential scanning calorimetry (DSC). Besides, the volatile emissions of the mixtures at high temperature have been estimated from loss weight measurements as a function of stored time

Experimental and numerical investigation of fracture mechanics of bitumen beams

This work presents an experimental and numerical investigation to characterise the fracture properties of pure bitumen (the binder in asphalt paving materials). The paper is divided into two parts. The first part describes an experimental study of fracture characterisation parameters of pure bitumen as determined by three-point bend tests. The second part deals with modelling of fracture and failure of bitumen by Finite Element analysis. Fracture mechanics parameters, stress intensity factor, KIC, fracture energy, GIC, and J-integral, JIC, are used for evaluation of bitumen's fracture properties. The material constitutive model developed by Ossa et al. [40,41] which was implemented into a FE code by Costanzi [18] is combined with cohesive zone models (CZM) to simulate the fracture behaviour of pure bitumen. Experimental and numerical results are presented in the form of failure mechanism maps where ductile, brittle and brittle-ductile transition regimes of fracture behaviour are classified. The FE predictions of fracture behaviour match well with experimental results. © 2012 Elsevier Ltd.

Pilot Plant Studies On The Utilization Of Industrial Wastes For Industrial Bitumen Manufacture

The main objectives of the investigations reported in the present thesis are the following: (1) to find out some industrial wastes as cheaper additives to augment the air-blowing polymerization process of bitumen. This will bring down the cost of production of industrial bitumen which can be applied for the manufacture of bitumenous paints, roofing and flooring materials etc. (2) to find out suitable promoters for the above additives. This will bring down the consumption of the additives (3) to help in the industrial pollution control (4) to investigate the usefulness of the industrial bitumen produced in the production of bituminous paints (5) to find out thekinetic parameters of the reactions invovled with different additives. This is essential for the design, construction and operation of new industrial bitumen plants using the additives investigated. This will also enable us to establish the mechanism of the reactions involved in the process

Organic geochemical studies of DSDP Leg 64 Holes

Twenty-six core samples from Leg 64, Holes 474, 474A, 477, 478, 479, and 481A in the Gulf of California, were provided by the Joint Oceanographic Institutions for Deep Earth Sampling (JOIDES) Advisory Panel on Organic Geochemistry for analysis. The high heat flow characteristic of the basin provides an opportunity to study the effect of temperature on the diagenesis of organic matter. The contents and carbon isotope compositions of the organic matter and bitumen fractions of different polarity, isoprenoid and normal alkane distributions, and the nature of tetrapyrrole pigments were studied. Relative contents of hydrocarbons and bitumens depend on the thermal history of the deposits. Among other criteria, the nature and content of tetrapyrrole pigments appear to be most sensitive to thermal stress. Whereas only chlorins are present in the immature samples, porphyrins, including VO-porphyrins, appear in the thermally altered deposits, despite the shallow burial depth. Alkane distributions in thermally changed samples are characterized by low values of phytane to 2-C18 ratios and an odd/even carbon preference index close to unity. The thermally altered samples show unusual carbon isotope distributions of the bitumen fractions. The data also provide some evidence concerning the source of the organic matter and the degree of diagenesis.